Red monazo wool dyes



Patented Oct.31, 1944 V 23 1 4 13 PATENTLT. .IOFFICE Donovan EfiKvalnes, Penns Grov'e, N. J assignpr to E. I. duPont de Nemours & company-g wllmington, Del., a corporation of Delaware No Drawing. Application November 18, 1941, Serial No. 419,528

This invention relates to monazo dyes which are suitable for dyeingr wool' in -shades of red and to processes of manufacturing the same, and

especially to monazo, dyes resulting from suit-,

'ably'coupling-'thei..diazos' of a class of "2-amino'=' r H033 di hen l-sulione's'with ammaacidbr'a class of ,o y t.

deprivatsiyves thereof I and ebuplin'g in mediagsuchethatlthe-woupling oce Red. Inonazohdyes for W001 have-heretofore t ii t???e m fils fones with 'gammaracid wherein'the monoacidyli, q F Q Wm -i substituted in thel-vsamabenzene rinvgi cludes' examples thatare givemas illusfinatweuamaieas the primary amino group?" Thedyin s ma bpdimenteeotxheninventiomendenoe:asmimita on wool with these 'dyes are undesirably blue and x tfi i l m dull in shade and"theit light fastnessis not en- 15 We1ghummessmthenmsemoted"'*"' tirely satisfactory. Red mon'azo dyes have been I Example? "1 I I phenyl-sulfone. These dyes have very good light the hydmmfmd? imggg fastness and shade, but it is desired to provide glphenylsmfone'area'ddedflmz' f r-- dyes which have a satisfactory and good light ter and '73 parts tofwhydrogen rch oridevmIcems M fastness and which operate to better advantage added to the stlrredimlxtur? to lower the P in neutral dyebaths. perature to 0-5 C. S1xty-n1ne parts of sodium It is among the objects of 'th'e*present invenmtnte. dlssolveimn .2wipartsopwatepare tion 'tozprovide monazo;idyesewhi'chiproduceiared'i325;? mpldly as dlafzotlzainon i i dyeings on wool that are very fastiatoilighfifanmo t for two fi g thattarerteapabletrofszdyeingswvell frommeutrapas 1s filtiered the Q W an t e wen" asifromfi acmsolufions theweofmAnnthe-rmbwh trate 1s treated with sulfamic ac1d-to destroy any ject=-ofthezinventioirisito providesuchzred mtmmQ excess litmus acid- A 239 Parts 0f azo-idyes'whichrdyewooliaecenomicallyafrom memoin 52500 parts of r a ter and 40 parts of sodium hydroxide is cooled tra baths and we bn h dyem s havin oodw o fasi mess to light? andwietitreatm ents. An o ther to d1 zfi g f i g fi agded object of the invention is toprovidetsuchldyes raplt so 1 5; g 8 x whichtmay'be used to'dye wooleconomicallyifro'in' fg a g g gg g g gg i zgfifigflg so acidbathspwhereinexcellent;transfeliof the-lovel est; f '1? Occurs and which-produce completely level and: dlum acetate solution. When the solution 15 no diamino diphenyl sulfones of the general typ lightmfastnes'sndwgoede fastnessftoeiw t f which are representediby the formula ents. It dyes wool fairly w n (about 40%)? a from a neutral solution. The dye is represented .19 e ormula with-l gammawacid or:tcertainmderivativesethereoiixo which:arevrepresentedrinageneralzbyatherformmamfi5 Example 2 Three hundred eighty-six and one-half parts or the hydrochloride of 2-amino-4'-benzoyl-amino-diphenylsulfone are used instead of the di-' azo component in the procedure described in Ex- Dyeings made on wool with this product have nearly the same shade as the dyeings made from the product of Examplel. However, this product has greater ability to dye wool from a neutral solution than the dye of Example 1.

Examples 1 sixty nine parts;v of sodiumgnitrite are added gradually below,,25- C.-=to:150 0 parts of monohydrate. Stirring is continueduntil a solution is obtained. Then 402, vparts of 2- aInino-4- (tolyl sulfonylamino) diphenylsu1fone are added gradually and the mixture stirred-at 25? C. for four hours. The solution is then poured upon ice and the diazo solutiontfilterem The latter is :added to a V S0111? tion of 2-amino-6-sulfow8-naphthol, as prepared in Example 1. Eightyr-two, parts of sodium acetate are added,,fol1owed' by theslow addition of sodium hydroxide, at-5i C1, to destroythe Congo acidity. Atthis point coupling is rapid; The dye is isolated as describ'ed in' Example L -The prod- 1 not is represented'by the formula 'Ilieproduct produces dyeings on wooljin red" shades'fhaving good fastness properties .i q me Byproceeding in accordance with Example 3 l but using 418 parts oi 2-amino-4'-(para-tolyl--' sulfonyl-methyl-amino) -diphenylsulfone insteadof the diazo component described-therein a product' is-obtained which is represented by the for- This product is quite suitable for the dyeing of wool under neutral conditions giving red shades of good fastness properties.

Example 5 By proceeding in accordance with Example 1 but using 356.5 parts of the hydrochloride of 2- amino' 4 carb'oethoxyamino diphenyl'sulfone instead of the'diazo component described therein, a dye is obtained which is represented by the formula IYIH:

OsNa 'tothe properties of the dye of Example 1.

Example 6 By proceedingin 'accordance withEXample 1 but using 253 parts of 2-methyl-amino-6-sulfo- 8-naphthol instead of the coupling component described therein, a product isobtained which is representedby the formula l i lTIHCHs product of'Example 1. y. l

' A dye similarto the above; described N-methyl derivativeis obtained by using 2-(hydroxy-ethylamino) -6-sulfo-8-naphthol as the coupling component :instead of 2-methyl-amino-6-sulfo 8 naphthol. 4 v

. v Example-7 1 v By proceeding in accordancewith Example 1 except that an equivalent amount of the hydro-- chloride of '2 -amino-2"-acetylI-amino diph'enylsulfone is used instead of the diazo. component shade and properties as those of the dye described in Example 1.,is produced. It is "repreeo ented bythefo rmula. f

-NHO dart SOsNa The diazo component was prepared by reacting ortho-nitro-chlor-benzene with one equivalent of sodiuni hydrogen suliide; followed by re- "actionwitha second-mole ofF ortho-nitro-chlon' 'Ihe' properties of this product are closelyysirnilar This product yields'bluer shades of'red than'thedescribedther'ein; a dye having'nearly the same also was prepared by condensing the sodium salt of para-acetyl-amino-benzene-sulfinic acid with ortho-nitro-chlor-benzene in an autoclave at 140-150 C. using. methyl alcohol as a solvent. The product thus obtained was *catalytically reduced.

The diazo components of Examples 2, 3 and 5 were prepared by use of benzoyl chloride, paratolyl-sulfonyl chloride and ethyl-chloro-formate in place of acetic anhydride at the appropriate point in the general procedure outlined above.

The diazo component of Example 4 was prepared by treating an alkaline solution of 2-nitro- 4para-to1yl-sulfonyl amino diphenyl sulfide with dimethyl-sulfate. This methyl derivative was oxidized to the sulfone and the nitro group reduced.

As illustrative of other primary arylamines which produce dyes having similar properties when used as diazo components in accordance with the foregoing examples are mentioned Z-amino-l'-propionyl-amino -diphenyl sulfone,

2-amino-4-para chlor-benzoylamino diphenyl-sulfone,

Z-amino-Q-carbomethoxy amino-diphenyl-sulfone,

2-amino-4-benzene -'sulfonyl amino diphenylsulfone,

Z-amino-l' -para-toly1sulfonyl-ethyleamino-- diphenyl-sulfone,

2-amino-4'-para-tolyl-sulfonyl-hydroxy ethylamino-diphenyl-sulfone,

2-amino-4'-paratolyl -wsulfonyl sulfato ethylamino-diphenyl-sulfone,

2-amino-4-para-tolyl-sulfonyl-carboxy-methyl- I Z-amino-W-chlor-acetyl amino diphenyl sulfone, Z-amino-Zabenzoyl-amino-diphenyl-sulfone and 2-aminoflfloenzene-sulfonyl amino diphenylj sulfo'ne.

'In the specification and claims the term, substituted alkyl groups, refers to the groups onzonzon, C2H4OSO3H, -CI-I2COO'H,

. C2I-I4SO3H and CH2C6H5 The only coupling components which can be used with the above described diazo components to produce combinations similar to those described are 2-amino-6-sulfo-8-naphthol, 2-methyl-amino-6-sulfo-8-naphthol, 2-ethyl-amino-6-sulfo 8 naphthol and 2-hydroxy-ethyl-amino-6-sulfo 8 naphthol.

2-amino-diphenylrsulfone derivatives coupled in acid mediumto 2-amino-6-sulfo-8-naphthol in general give red dyes of good light fastness on wool. Their level-dyeing and good transferring properties decrease and their wet fastness and ability to dye under neutral conditions increase approximately with the increasing size of substituent groups, provided the latter do not produce solubility in water. It has been found that the presence of such groups as nitro, amino, substituted amino and alkoxy groups in the benzene ring containing the azo group deepens the shade and decreases the light fastness of the dyes with respect to the parent structure. In the dyes of 'the present invention, the substituted amino groups are in the benzene ring of the diphenylsulfone which is'not connected to the azo group. Accordingly it has been found that these groups exert little effect on the shade or light fastness of the parent structure but do not affect the neutral dyeing strength of the parent structure'particularly.

Accordingly any 2-amino-diphenyl sulfone can be used as the amino base which is represented by the formula is. one of a group consisting of monoand disubstituted amino groups in which X is one of a group consisting of hydro-gen, alkyl having 1 to 4 carbons and substituted alkyl; Y is one of a group consisting of '(fi"alkyl of the benzene series,

-([.?methoxy 7-6; phenyl-sulfone tolyl-sulfone and naphthyl-sul-.

fone, wherein alkyl is from a group consisting o1 saturated and unsaturated aliphatic groups having 1 to 2 carbons and the mono-chloro, -pheny-l; -phenoxy and -carboxy derivatives thereof and aryl is from a group consisting of phenyl; tolyl, monochloro phenyl, monosulfo phenyl and monocarboxy phenyl. Dyes having properties similar to those specifically described are produced by coupling these diazotized bases with any of the coupling components represented by the formul Lira wherein Z is one of a group consisting of-hydro gen, methyl, ethyl and hydroxyethyl.

The described. dyes give good level dyeings on wool fromneutral as well as from acid baths. The red shades produced thereby have excellent light fastness and other good general fastness properties desired in Wool dyeings. The pre-v ferred modifications are those in which the coupling component is 2-amino{8-naphthol 6-sulfonic acid since they have the best lightfastness and the shades of the dyeings are not as deep as those inwhich the amino group is alkylated. Among these, the modifications wherein the sulfone group is para substituted are the most desirable. i v From the foregoing disclosure it will be recognized thatthe invention is susceptible of modifi-' cation without departing from the spirit and scope thereof and it is to be understood that the invention is not restricted to the specific illustrations thereof herein set fort 'I-claim: I x 1. An azo dye which is represented in its acid form by the formula SO: H-

wherein is one of a group consisting of monoand di-substituted amino groups in which X is one of a group consisting of hydrogen, alkyl having 1 to 4 carbons, hydroxy ethyl, sulfato ethyl, sulfo ethyl,

carboxy methyl and benzyl; Y is one of a group consisting of %metlioxy phenyl-sulfone, tolyl-sulfone, naphthyl-sulfone, C-R

in' which R is one of the group consisting of alkyl having I .to 2 "carbons and the mono-chloro, phenoxy and -carboxy derivativesthereofand TF I in which R is one of the group consisting of phenyl, :tolyl, monochloro-phenyl, monosulfophenyl and monocarboxy-phenyl; and Z is one of the group consisting of hydrogen; methyl, ethyl is one of a group consisting of monoand di-substituted amino groups in which X is one of a group consisting of hydrogen, alkyl having 1 to 4 carbons, hydroxy ethyl, sulfato ethyl, sulfo ethyl, carboxy methyl and benzyl; Y is one of a group consisting of phenyl-sulfone, tolyl-sulfone, naphthyl sulfone;

\ in which R is one of the group consistingof alkyl having 1 to 2 carbons and the mono-chloro,

' phenoxy and -carboxy derivatives thereof and snail 7 is one of a group consisting of monoand di-subpresented in'its acid stituted-amino groups in which X is one of a group consisting'of hydrogen, alkyl'having 1 to 4 carbons, .hydroxy ethyl, sulfato ethyl, sulfo ethyl, carboxy methyl and benzyl; Y is one of a group consisting of 5- fi-methoxy -G- ethoxy phenyl-sulione, to1y1-su1fone,. naphthyl-sulfone,

, in,which,R is oneof the group consisting of alkyl having ,1 to 2 carbons and the mono-chloro, phenoxy and -carboxy derivatives thereof and I fi in which R is one of the group consisting of phenyl, tolyl, monochloro-phenyl, monosulfophenyl and monocarboxy-phenyl; and Z is one of 5 the group consisting of hydrogen, methyl, ethyl and hydroxy ethyl.

4. An azo dye which is represented in its acid form by the formula so, H0 Q SOaH if-(fi-(JH;

5. An azo dye which is represented in its acid form by the formula IIIHz s02 HO- f s 03H 1 lI(l3I-OC2H H o 6. An azo dye which is represented in its acid form by the formula 7. The process which comprises diazotizing a 2-amino-diphenyl sulfone represented by the wherein is oneof a group/consistingof monoand di-substituted amino groups, in which X is one of a group consisting ofhydrogemalkyl having .1 to 4, carbons, hydroxy ethyl, sulfatoethyi, sulfo ethyl, carboxy methyl and benzyl; Y is one of a group consisting of l -%ethoxy 0 phenyl-sulfone, tolyl-sulfone, naphthyl-sulfone,

in which R is one of the group consisting of alkyl having 1 to 2 carbons and the mono-chloro, phenoxy and -carboxy derivatives thereof and H 0 in which R is: one of the group consisting. of phenyl, tolyl, monochloro-phenyl, monosulfophenyl and monocarboxy-phenyl; and Z is one of the group consisting of hydrogen, methyl, ethyl and hydroxy ethyl; and coupling in a coupling medium with an 8-naphthol-6-sulfonic acid represented by the formula SOsH wherein Z is one of a group consisting of hydrogen, methyl, ethyl and hydroxyethyl; said coupling medium being adjusted so that the coupling occurs in the position indicated by the sym- 1001 -H.

8. The process which comprises diazotizing a 2- amino-diphenyl sulfone represented by the stituted amino groups in which X is one-of a group consisting of hydrogen, alkyl having 1 to 4 carbons; hydroxy ethyl, sulfato ethyl, sulfo ethyl, carboxy methyl and benzyl; is one of a group consisting of l I phenyl-sulfone, toIyl-sulfone, naphthyl-sulfone, R

is one of a group consisting of monoand di-subphenyl, tolyl, monochloro-phenyl, monosulfophenyl and monocarboxy-phenyi; and Z isoneiof the group consisting of hydrogen, methyl, ethyl and hydroxy ethyl; and coupling in a coupling medium with an 8-naphthol-6-sulfonic acid represented by the formula wherein Z is one of a. group consisting of hydrogen, methyl, ethyl and hydroxyethyl; said cou pling medium being adjusted so that the coupling occurs in the position indicated by the sym b01H.

DONOVAN E. KVALNES. 

